O-alkyl-s-(beta-alkoxyethyl)-s-(alkoxy or phenoxy-alkyl) phosphorodithiolates

ABSTRACT

O-ALKYL-S-(B-ALKOXYETHYL)-S-(ALKOXY OR PHENOXYALKYL)PHOSPHORO DITHIOLATES OF THE GENERAL FORMULA   R&#39;&#39;-O-P(=O)(-S-A-O-R3)-S-C2H4-O-R2   IN WHICH R1 IS METHYL OR ETHYL, R2 IS LOWER ALKYL, R3 IS LOWER ALKYL OR   (X)N-PHENYL   WHEREIN N IS 0 TO 3 AND X IS HALOGEN, LOWER ALKYL OR NITRO, AND A IS LOWER ALKYLENE, WHICH POSSES INSECTICIDAL, ACARICIDAL AND NEMATOCIDAL PROPERTIES.

United States Patent 3,793,409 O-ALKYL S (fl-ALKOXYETHYD-S-(ALKOXY 0RPHENOXY-ALKYL) PHOSPHORODITHIOLATES Shigeo Kishino, Tokyo, and AkioKudamatsu and Kozo Shiokawa, Kanagawa, Japan, assignors to BayerAktiengesellschaft, Leverkusen, Germany No Drawing. Filed Nov. 8, 1971,Ser. No. 196,748 Claims priority, application Japan, Nov. 18, 1970,45/100,996 Int. Cl. C07f 9/16; A01n 9/36 U.S. Cl. 260-951 9 ClaimsABSTRACT OF THE DISCLOSURE O-alkyl-S- (fl-alkoXyethyl)-S- (alkoxy orphenoxyalkyD- phosphoro dithiolates of the general formula 0 SCzH4ORRIO-P S-A-OR (I) in which R is methyl or ethyl, R is lower alkyl, R islower alkyl or wherein n is 0 to 3 and X is halogen, lower alkyl ornitro, and A is lower alkylene,

which possess insecticidal, acaricidal and nematocidal properties.

The present invention relates to and has for its objects the provisionof particular new O-alkyl-S- (B-alkoxyethyh- S-(alkoxy orphenoxy-alkyDphosphoro dithiolates wherein the phenyl radical, ifpresent, may be substituted by up to three halogen, alkyl or nitrogroups, which possess insecticidal, acaricidal and nematocidalproperties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew way especially for combating pests, e.g. insects, acarids andnematodes, with other and further objects becoming apparent from a studyof the within specification and accompanying examples.

From the specification of Dutch Pat. No. 67/ 17383 it is known that thecompound of the formula has insecticidal and fungicidal activities.

The present invention provides, as new compounds, the phosphoric acidesters of the general formula 0 S 0 11 0 IR.

R O-P S-A-OR in which R is methyl or ethyl, R is lower alkyl,

R is lower alkyl or wherein X is halogen, lower alkyl or nitro, and A islower alkylene.

3,793,409 Patented Feb. 1'9, 1974 moon-14s s in which M is a metalequivalent or an ammonium group is reacted with a halide of the generalformula in which Hal is halogen, preferably chlorine or bromine, or (b),as a preferred alternative in those cases where R is identical to R andA is ethylene, a mercaptan of the general formula I-ISC H OR (IV) isreacted, in the form of a metal or ammonium salt thereof or in thepresence of an acid-binding agent, with a phosphoric acid esterdichloride of the general formula In the foregoing Formulas H to V, R R'R and A have the meanings stated for Formula I.

Preferably, the reactants are used in substantially amounts shown in thebelow-mentioned reaction scheme.

In either of the process variants of this invention, the reaction ispreferably carried out in the presence of a solvent or diluent. For thispurpose, all inert solvents or diluents are suitable, especially water;aliphatic, alicyclic and aromatic optionally chlorinated hydrocarbonssuch as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene,xylenes, methylene chloride, chloroform, carbon tetrachloride, mono-,diand tri-chloroethylenes and chlorobenzene; ethers, such as diethylether, methylethyl ether, di-isopropyl ether, dibutyl ether, ethyleneoxide, dioxane and tetrahydrofurane; ketones, such as acetone,methylethyl ketone, methylisopropyl ketone, and methylisobutyl ketone;alcohols such as methanol, isopropanol, butanol and ethylene glycol;nitriles such as acetonitrile, propionitrile and acrylonitrile; esterssuch as ethyl acetate and amyl acetate; acid amides such as dimethylformamide and dimethyl acetamide; and sulfones and sulfoxides such asdimethyl sulfoxide and sulfolane.

In either of the above process variants the reaction may be effected attemperatures within a fairly broad range: generally, the reaction iscarried out at from 'above 20 C. to the boiling point of the reactionmixture, preferably at from about 0 to C. or to the boiling point of thereaction mixture, whichever is the lower.

Both process variant (a) and process variant (b) are preferably carriedout under atmospheric pressure, although it is possible to conducteither reaction under elevated or reduced pressure.

The reaction process variant (a) is illustrated by the followingequation:

/P M Hal-A-OR R 0 01H; s 's (III) RXO 0 P-SAOR3 M Hal R20 CzH S (I) inwhich R R R A and M have the meanings stated above. M is preferablyammonium or an alkali metal.

As examples of the dithiophosphates of the Formula 11, there may bementioned the potassium, sodium and ammonium salts of'O-methyl-S(fi-ethoxyethyl)-dithiophosphoric acid,O-ethyl-S-(B-methoxyethyl)-dithiophosphoric acid, O-ethyl S(B-ethoxyethyl)-dithiophosphoric acid,O-ethyl-S-(.B-isopropoxyethyl)-dithiophosphoric acid andO-et-hyl-S-(fi-n-butoxyethyl)-dithiophosphoric acid.

As examples of the halides of the Formula III, there may be mentioned4-chlorophenoxymethyl chloride, 2,4- dichlorophenoxy methyl chloride,B-methoxyethyl chloride, fl-ethoxyethyl chloride, fl-isopropoxyethylchloride, fi-n-butoxyethyl chloride, B-phenoxyethyl chloride, fi-(Z-chlorophenoxy)ethyl chloride, [3- (4-chlorophenoxy)-ethyl chloride,B-(2,4-diohlorophenoxy)ethyl chloride, 8-(2,4,S- trichlorophenoxy)ethylchloride, (4 tert. butylphenoxy)ethyl chloride,B-(3-methyl-4-chlorophenoxy)ethyl chloride, fi-(4-nitrophenoxy)ethylchloride, -y-phenoxypropyl chloride and the corresponding bromides.

The reaction of process variant (b) is illustrated by the followingequation:

in which R and R have the meanings stated above, and M is hydrogen,ammonium or a metal, preferably an alkali metal.

As examples, of the phosphoric acid ester dichlorides of the Formula V,there may be mentioned O-methylphosphoric acid dichloride andO-ethylphosp-horic acid dichloride. As examples of the mercaptans of theFormula IV,' there may be mentioned fl-metihoxyethyl mercaptan,fl-ethoxyethyl mercaptan, B-isopropoxyethyl mercaptan andfl-n-butoxyethyl mercaptan; the sodium, potassium and ammonium salts ofthese mercaptans are also suitable.

As stated above, process variant (b) may be carried out in the presenceof an acid-binding agent according to need. As the acid-binding agentthere may be used a hydroxide, carbonate, bicarbonate or alcoholate ofan alkali metal, or a tertiary amine, such as trieth'ylamine,dimethylaniline or pyridine. When the reaction is carried out in theabsence of an acid-binding agent, the intended product can be obtainedby forming in advance a. salt, preferably an alkali metal or ammoniumsalt, of the appropriate mercaptan and then reacting the salt with theappropriate O-alkyl phosphoric acid dichloride.

The compounds of this invention, as implied above, exhibit excellentbiological activities against various harmful insects, spider mites andnematodes. llnsecticidally, the compounds of this invention appear to besuperior to the known compound of the Formula A given above and to otherknown compounds having similar directions of activity.

Furthermore, the active compounds of this invention exhibit only a verylow toxicity towards warm-blooded animals and show no phytotoxicitytowards cultivated plants. They are characterized by an activity thatsets in quickly and that is long-lasting. Accordingly, they can be usedfor controlling harmful insects, such as biting and sucking insects,mites and nematodes in agriculture.

For instance, the active compounds of this invention are effective forcontrolling insects belonging to the Coleoptera such as the rice weevil(Sitophilu's oryzae), flour beetle (T ribolium castaneum),tWenty-eight-spotted lady beetle (Epilachna vigintioctopunctata), barleywireworm (Agrotes fusicicollis) and soy bean beetle (Anomalarufocuprea); insects belonging to the Lepidoptera such as the gypsy moth(Lymantria dispar), tent caterpillar (Malacosoma neustria testacea),common cabbageworm (Pieris rapae crucivora), cotton worm or tobaccocutworm (Prodenia litura), rice stem borer (Chile suppressalis), smallertea tortrix (Adoxophyes orana) and almond moth (Ephestz'a cautella);insects belonging to the Hemiptera such as the green rice leaf-hopper(Nephotettix cincticeps), brown planthopper (Nilaparvata lugens),comstock mealybug (Pseudococcus comstocki), arrowhead scale (Unaspisyanonensis), green peach aphid (Myzus persicae) apple aphid (A phispomi) and cabbage aphid (Brevicoryne brassicae); insects belonging tothe Orthoptera such as the German cockroach (Blattella germanica)American cockroach (Periplaneta americana) and African mole cricket(Gryllotalpa africana); insects belonging to the Isoptera such as theJapanese termite (Leucotermes speratus); insects belonging to theDiptera such as the house fly (Musca domestica vicina) yellowfevermosquito (Aedes aegypti), seedcorn maggot (Hylemya platura), northernhouse mosquito (Culex pipiens), Chinese malaria mosquito (Anophelessinensis) and smaller house mosquito (Culex tritaeniorchynchus); mitessuch as the two spotted spider mite (Tetranychus telarius), citrus redmite (Panonychus citri) and Japanese citrus rust mite (Aculuspelekassi); and nematodes such as the southern root-knot nematode(Meloidogyne incognita), rice white-tip nematode (Aphelenchoidesbesseyi) and soy-bean c'yst nematode (Heteroa'era glicines).

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide formulations or compositions such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as halogenated hydrocarbons, e.g. freon; inertdispersible liquid diluent carriers, including inert organic solvents,such as aromatic hydrocarbons (e.g. benzene, toluene, xylene,dimethylnaphthalene, aromatic naphtha, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (e.g., chlorobenzenes, etc.),aliphatic and alicyclic hydrocarbons e.g., n-hexane, cyclohexane,gasolines for industrial use such as petroleum ether and solventnaphtha, and petroleum fractions such as parafiin wax, kerosene, lightoil, middle oil and heavy oil, halogenated aliphatic hydrocarbons (e.g.,methylene chloride, ethylene dichloride, carbon tetrachloride,trichloroethylene, ethylene dibromide, etc.), alcohols (e.g., methanol,ethanol, propanol, butanol, ethylene glycol, etc.), amines (e.g.,ethanolamine, etc.), ethers, (e.g., ethyl ether, ethylene oxide,dioxane, etc.) ether-alcohols (e.g., glycol monomethyl ether, etc.),esters (e.g., ethyl acetate, amyl acetate, etc.), amides (e.g., dimethylformamide, dimethyl acetamide, etc.), sulfoxides (e.g., dimethylsulfoxide, etc.), ketones (e.g., acetone, isophorone, methyl ethylketone, cyclohexanone, etc.), and/or water; as well as inert dispersiblefinely divided solid carriers, such as vegetable powders, ground naturalminerals (e.g., kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montomorillonite, kieselguhr,pyrophyllite, mica, gypsum, calcite, vermiculite, dolomite, muscovite,apatite, slaked lime, magnesium hydroxide, sulfur and pumice and groundsynthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g.,alkali silicates, synthetic alumina, etc.), synthetic resins such asphenol, urea and vinyl chloride resins; whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g., surface-active agents, for this purpose: emusifying agents, suchas nonionic and/ or anionic emulsifying agents (e.g., polyethylene oxideas well as ether and esters thereof such as polyoxyethylene esters offatty acids such as sorbitan monolaurate polyethylene oxide ethers offatty alcohols and alkyl phenols, alkyl sulfates such as sodium laurylsulfate, alkyl sulfonates, iaryl sulfonates, alkyl aryl sulfonates suchas sodium alkyl naphthalene sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.);cationic surfactants such as alkyl amines (e.g. lauryl amine, stearyltrimethyl ammonium chloride and alkyl dimethyl benzyl ammonium chloride)and polyoxyethylene alkyl amines; amphoteric surfactants; and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/ or liquid dispersiblecarrier vehicles and/ or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides and nematocides, or fungicides, bactericides, rodenticides,herbicides, fertilizers, growth-regulating agents, or antiviral agentswhich classes of materials include organic phosphorus acid esters,carbamates, dithio-(or thioD-carbamates, chlorinated organic compounds,dinitro compounds, organosulfur or organometal compounds, antibiotics,substituted diphenyl ethers, ureas and triazines.

The novel compounds may also be combined with adjuvants such as organicmatter, stabilizers, adhesive agents, .for example agricultural soap,calcium caseinate, sodium alginate, polyvinyl alcohol, detergents,coumarone (or indene) resins or polyvinyl butyl ether, combustiblematerials (for fumigants), for example zinc dust or dicyandiamide,oxygen-yielding substances, for example perchlorates, nitri-tes ordichromates, phytotoxicity-reducing substances, for example zincsulfate, ferrous chloride or copper nitrate, substances for prolongingthe biological effect, for example chlorinated terphenyls,emulsion-stabilizing substances, for example casein, gum tragacanth andcarboxymethyl cellulose (polyvinyl alcohol also being suitable for thispurpose), and synergistic agents.

The novel compounds may be applied in the form of particular dosagepreparations for specific application made therefrom, such as solutions,liquors, emulsions, suspensions, wettable powders, wettable tablets,soluble powders, pastes, dusts, granules, fumigating agents and smokingagents which are thus ready .for application in any usual manner, forinstance by spraying such as liquid spraying, misting, atomizing,dusting, scattering, watering, pouring, fumigating, soil applicationsuch as mixing, sprinkling, vaporizing and irrigating, surfaceapplication such as painting, banding and dressing (dust-coating),dipping and baiting.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.195% by weight, andpreferably 0.590% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.000120%, preferably 0.00510%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/ or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g., a surfaceactive agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.0001%, and preferably 0.00595% by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e., mist form, for example by airplane crop sprayingtechniques. 'Only up to at most about a few liters/hectare are needed,and often amounts only up to about 30 to 1000 g./hectare, preferably 300to 6000 g. lrhect'are, are sufficient. In this process it is possible touse highly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the active substance alone, e.g., about 20100% byweight of active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g., insects, acarids andnematodes, which comprises applying to at least one of correspondingly(a) such insects, (b) such acarids, (0) such nematodes, and (d) thecorresponding habitat thereof, i.e., the locus to be protected acorrespondigly combative or toxic amount, i.e., an insecticidally,acaricidally or nematocidally effective amount of the particular activecompound of the invention alone or together with a carrier vehicle asnoted above.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The preparation of the particular new compounds of the present inventionand their unexpected superiority and outstanding activity areillustrated, without limitation, by the following examples:

EXAMPLE 1 27 g. of potassium O-ethyl-S-(fl-ethoxyethyhdithiophosphatewere dissolved in 100 ml. of ethanol and 27 g. of2,4-dichlorophenoxyethyl bromide were added to the solution. Then, themixture was agitated at 75 C. for 3 [hours to complete the reaction. Theresulting inorganic salt was separated by filtration, and the ethanolwas distilled off from the filtrate under reduced pressure. ml. ofbenzene were added to the residue, and the mixture was washed with waterand 1% potassium carbonate, and dried over anhydrous sodium sulfate.Distillation of henzene gave 37 g. of a colorless oil,O-ethyl-S-(B-ethoxyethyl)-S [p (2,4- dichlorophenoxy)ethyl]phosphorodithiolate, having a refractive index n of 1.5690 and havingthe formula:

- 7 EXAMPLE 2 A mixture of 10.6 g. of ,B-ethoxyethyl mercaptan, 10.1 g.of triethylamine and 150 ml. of benzene was cooled to below 5 C. and16.3 g. of O-ethylphosphoric acid di- The pesticidal compositions ofthis invention are illustrated in and by the following examples, inwhich the active compounds are identified by the numbers assigned tothem in Examples 1-3.

EXAMPLE 4 chloride were added dropwise to the mixture with agita- 5tion. After completion of the dropwise addition the tem- 15 parts ofCompound No. 20, 80 parts of a 1:5 mixperature of the mixture wasgradually raised and the mixture of diatomaceous earth and kaolin and 5parts of ture was agitated at 70 C. for 1 hour to complete the reanemulsifier Runnox (a polyoxyethylene alkylaryl action. The reactionmixture was then cooled to room temether) were ground and mixed togetherto form a wetperature, washed with water, 1% hydrochloric acid and 10table powder. It was diluted to 0.05% before application. 1% potassiumcarbonate, and dried over anhydrous sodium sulfate. Distillation ofbenzene gave 26 g. of 0- EXAMPLE 5 ethyl-S,S-di-(p-ethoxyethyl)phosphorodithiolate boiling 30 parts of Compound lfio. 4, 30 parts ofxylene, 30 at 141-144 C. under 0.1 mm. 'Hg, having a refractive parts ofKawakazol (a high-boiling-point aromatic hyindex n of 1.5000 and havingthe formula: 15 drocarbon), and 10 parts of an emulsifier Sorpol (a oSCaHOCH polyoxyethylene alkylaryl ether) were mixed with stirring toform an emulsifiable preparation. It was diluted Gino-P to 0.05% withwater before application.

S CzH4O 02H:

Compounds synthesized by similar methods to those of 2 parts of CompoundN0. 5 and 98 parts of a 1:3 the foregoing examples are shown in Table 1.mixture of talc and clay were ground and mixed together TABLE 1 0SCIHQORZ R O-P S-A-O IR Compound Physical number R A R IR constants C2H4C2116 C2115 11.13 1.5107. C2H4 0 H3 H3 m3 1.5152 CzH4 CH3 CgHs 1m"1.5039 C2H4 CzHs 03117-180 an 1.4918 C2114 CaH7-1SO CaHr-iSO 11.131.4900 1 2H4 CiHn-n OAHD'H. 72D 1.4881

011, 01H Q m)" 1.5535

CH: 01H; 01 my 1.5639

10 01H! CIHI 02H Q 'nn"1.5413

11 CzHi CnHl CzHs Cl m)1.5572

12 CaHb CzHl CzHs Q 01 13 1-5541 13 01H; 02H; CaHriSO do 111. 1.5520

14 CH: CzH4 CzHu C1 1m" 1.5770

Minx-3.1:; C2115 C2111 CzHl C1 1m" 1.5780

17...: CgHs 03H 02H; fln 1.5350

Q-CaHn-tett;

18-..;.=:.:.. 01H; 02H. 0 H; 0H, m" 1.5575

19-...7.-..-;.- 02H; CzH| C2H| fln' 1.5695

20...: 03H; .CaHa 01H; Q fin 1.5414

to form a dust. This was applied by scattering via dusting equipment.

EXAMPLE 7 1.5 parts of Compound No. 19, 2 parts of an organic phosphoricacid ester, 0.5 part of isopropyl hydrogen phosphate and 96 parts of a1:3 mixture of talc and clay were ground and mixed together to form adust. This was applied by scattering via dusting equipment.

EXAMPLE 8 95 parts of clay particles of a size distribution of 0.2-2 mm.were put into a rotary mixer and a solution of 5 parts of compound No. 6in an organic solvent was sprayed onto the particles being rotated,thereby wetting the particles homogeneously. The particles were thendried at 40-50 C. to form coated granules. They were applied byspraying.

EXAMPLE 10 0.5 part of Compound No. 12, parts of Velsicol (ahigh-boiling-point aromatic hydrocarbon) and 79.5 parts of Deobase(deodorized kerosene) were mixed with stirring to form an oilpreparation. It was applied by spraying.

Nata-The term parts used in the Examples (4) to (10) means weight.

The excellent pesticidal activity of the compounds of this invention isillustrated in and by the following test examples, in which the activecompounds are identified by the numbers assigned to them in Examplesl-3.

EXAMPLE 11 Test on effects against tobacco cutworm larvae: Preparationof sample formulation.-

Solvent: 3 parts by weight of dimethyl formamide. Emulsifier: 0.1 partby weight of alkylaryl polyglycol ether.

In order to prepare a suitable formulation of an active compound, onepart by weight of the active compound was mixed with the above amount ofthe solvent containing the above amount of the emulsifier, and themixture was diluted with water to form an aqueous formulation containingthe active compound at a prescribed concentration.

Test procedure.--Sweet-potato leaves were dipped in a formulation of anemulsifiable liquor containing the active compound at the prescribedconcentration, and they were then dried in air and placed in a 9 cm.diameter Petri dish. Then 10 third-instar tobacco cutworm (Prodenialitura) larvae were put into the dish and the dish was kept in athermostat chamber maintained at 28 C. After 24 hours had passed, thenumber of dead larvae was counted and the killing ratio was calculated.The results are shown in Table 2.

1 0,0-dimethy1-O- (3-methyl-4-methylmercaptophenyl) phosphorothioate.

TABLE 2 Killing ratio Active ingredient concentration 300 p.p.m. 100p.p.m.

Compound number' Notes:

Compound:

(B C2H50\(]I[) /PSOHzCHz-O- C zHsO CH: S

/PSCH3CH1O CzHsO 011201120 23 CzHsO O l] /P-S-CHzCHg-O Q0 onion: s

(E) canto o ll /P-S -CH2-O Cl Cz'HsO CH2 S ll /P-S -CHz-O C1 CzHsOCHaCHzCHzS C2H5O O /P-S-CH1-O Cl o ornorn s P-S-CHz-OCH5 C2H50 CH2 SC2H50\[j P-S--CH2CH2CHz-O-C2Hs C2H5O CHzCHaCHzS Sumithion:0,0-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate, commerciallyavailable comparison.

EXAMPLE 12 Test on efiects against house flies:

Test Procedure.-A sheet of filter paper was spread in a Petri dish of 9cm. diameter and 1 ml. of an aqueous formulation containing the activecompound at the prescribed concentration and prepared in the same manneras in Example 11 was poured into the dish. Then 10 female house-flyimagines were put into the dish and the dish was kept for 24 hours in athermostat chamber maintained 1 1 at 28 C. The number of the dead flieswas then counted and the killing ratio was calculated. The results areshown in Table 3.

Test on effects against adzuki bean weevils:

Test procedure.Ten adzuki bean weevils were soaked for 1 minute in anaqueous formulation containing an active compound at a prescribedconcentration and which had been prepared in the same manner as inExample 11, and they were then kept in a thermostat chamber maintainedat 28 C. The number of dead weevils was counted after 24 hours hadpassed and the killing ratio was calculated. The results are shown inTable 4.

TABLE 4 Killing ratio (percent) Active ingredient concentration 1,000p.p.m. 100 p.p.rn.

Compound number:

Compound (A) 20 EXAMPLE 14 Test on effects against carmine mites:

Test procedure.Kidney bean having two developing leaves and plan-ted ina 6 cm. diameter pot was infested with 50-100 imagines of the carrninemite. Two days after the infesting, an aqueous formulation of anemulsifiable liquor containing the active compound :at a prescribedconcentration and which had been prepared in the same manner as inExample 11, was sprayed in an amount of 40 ml. per pot. Each pot waskept in a greenhouse for days and the control effect was evaluated onthe following scale:

Index.

3: No living imago 2: less than 5% of living imagines compared to anuntreated control 1: 550% of living imagines compared to the untreatedcontrol 0: more than 50% of living imagines compared to the untreatedcontrol.

The results are shown in Table 5.

TABLE 5 Control efiect index 1,000 ppm. 300 p.p.m.

Compound number:

4 3 2 6 3 2 12. 3 3 19. 3 2 Sappilan* (CPCBS) 3 2 Compound (A) 0 0'Sappilan=0hlorophenyl chlorobenzenesulionate, commercially available.

1-2 EXAMPLE 15 Test on effects against root-knot nematodes:

Preparation of sample formulation-2 parts by weight of an activecompound were mixed with 98 parts by weight of talc, and the mixture wasground to form a dust.

Test procedure.The formulation as prepared above was mixed with soiltainted with sweet-potato root-knot nematodes in an amount such that aprescribed concentration of the active compound was obtained in thesoil. The treated soil was stirred and mixed until uniform, and then itwas packed into pots each having an area of l/SOOO are. Thereafter,about 20 tomato seeds (Kurihara variety) were sown per pot andcultivated for 4 Weeks in a greenhouse. Then each root was drawn outfrom the soil without damaging it. The damage degree caused by thenematodes was evaluated with respect to 10 roots as one group based onthe following scale.

Z(rank value) (rank population) Knot Index- (Whole population examined)X4 The results are shown in Table 6.

TABLE 6 Effects against root-knot nematodes Knot index (percent) 3 5 30p.p.m. l5 p.p.m.

Compound number 4"..- 0 1. 7 0 3. 5 Terracur-p 0. 8 15. 2

Terracur-p: 0, O-diethyl-O- (4-methylsulfinylphenyl)-phosphorothioate.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. Phosphoric acid esters of the general formula 0 SCQH4OR2 RIO-P SAO R8(I) in which R is methyl or ethyl, R is lower alkyl, R is lower alkyl orwherein n is 0 to 3 and X is chlorine, lower alkyl or nitro, and A islower alkylene.

2. Compounds according to claim 1, in which R is methyl or ethyl, R is C-C alkyl, R is C -C alkyl, phenyl or phenyl substituted by chlorine, C-C alkyl or nitro, and A is methylene, ethylene, propylene, trimethyleneor tetramethylene.

3. The compound according to claim 1 wherein such compound is O-ethyl-S-(fl-methoxyethyl)-S-(,B-ethoxyethyl) phosphorodithiolate of the formula13 4. The compound according to claim 1 wherein such compound isO-ethyl-S,S-di-(fl-ethoxyethyl) phosphorodithiolate of the formula SCIHOC H CzH O- S C1340 (31H; 5. The compound according to claim 1 whereinSuch compound is O-ethyl-S-(fi-isopropoxyethyl)-S-(B-ethoxyethyl)phosphorodithiolate of the formula 0 SC2 40C2Hs C1H|OP S01E40 01111-150(5 6. The compound according to claim 1 wherein such compound isO-ethyl-S,S-di-(fi-isopropoxyethyl) phosphorodithiolate of the formula(II) SCaHAO CrHr-iso C:H|OP

S CgHrO C |H7lSO (6) 7. The compound according to claim 1 wherein suchcompound is O-ethyl-S-(p-phenoxyethyl)-S-(flethoxyethyl)phosphorodithiolate of the formula 0 SCI-H40 01H;

8. The compound according to claim 1 wherein such compound isO-ethyl-S-[fl-(4-ohlorophenoxy)ethyl]-S-(6- ethoxyethyl)phosphorodithiolate of the formula s mum-Q01 s mmoQ-no.

References Cited UNITED STATES PATENTS 1/1972 Tsuchiya et a1. 260950 XRANTON H. SU'ITO, Primary Examiner US. Cl. X.R. 260-950; 424-217

